Copper–Oxygen Dynamics in the Tyrosinase Mechanism

The dinuclear copper enzyme, tyrosinase, activates O₂ to form a (μ-η²:η²-peroxido)dicopper(II) species, which hydroxylates phenols to catechols. However, the exact mechanism of phenolase reaction in the catalytic site of tyrosinase is still under debate. We herein report the near atomic resolution X-ray crystal structures of the active tyrosinases with substrate l -tyrosine. At their catalytic sites, CuA moved toward l -tyrosine (CuA1 → CuA2), whose phenol oxygen directly coordinates to CuA2, involving the movement of CuB (CuB1 → CuB2). The crystal structures and spectroscopic analyses of the dioxygen-bound tyrosinases demonstrated that the peroxide ligand rotated, spontaneously weakening its O−O bond. Thus, the copper migration induced by the substrate-binding is accompanied by rearrangement of the bound peroxide species so as to provide one of the peroxide oxygen atoms with access to the phenol substrate's ϵ carbon atom.     

Hartree–Fock and density functional theory calculations for the reaction mechanism of nitric oxide reductase cytochrome P450nor from Fusarium oxysporum

A reaction mechanism of a nitric oxide reductase, cytochrome P450nor (P450nor) from Fusarium oxysporum, was clarified by using Density functional theory and Hartree–Fock calculations. In this reaction mechanism, molecular orbital (MO) analysis revealed that the NO ligand dissociates from the heme iron immediately after one-electron reduction by NADH, and MO energy analysis revealed that NADH acts as a one-electron reducer, not as a two-electron reducer, and that NADH has a pivotal role different from other one-electron reducers. The role of NADH is to act as a double one-electron donor (i.e. one-electron transfer occurring twice) and to combine with the NO⁻ molecule by charge recombination reaction. Our quantum chemical calculations indicated that all reactions occurring in the heme pocket are too fast to become rate-limiting. Therefore, the rate-limiting steps in the proposed reaction mechanism are the process of capturing NO and NADH into the heme pocket and the process of expelling a product generated in the heme pocket. Kinetics of these processes was discussed based on large-amplitude vibration, which helps capturing and expelling processes in a widely opened heme pocket of P450nor. The reaction mechanism proposed here well explains published experimental data.     

Solubilization of lanthanide ions by cyclodextrins in basic aqueous solutions

Cyclodextrins form complexes with lanthanide ions in basic aqueous solutions. This complex formation in basic solution dramatically enhances the solubility of lanthanide ions, which are otherwise insoluble due to the formation of hydroxide gels. Solutions of the -cyclodextrin-Ce³⁺ complex effectively hydrolyze 2-deoxyadenosine-5-monophosphate to 2-deoxyadenosine.     

Direct observation of the one-electron reduction of methyl viologen mediated by the CO2 radical anion during TiO2 photocatalytic reactions

The one-electron reduction of methyl viologen (MV(2+)) mediated by the carbon dioxide radical anion (CO(2)(*-)) during photocatalytic reactions in a colloidal TiO(2) aqueous solution (pH 2) has been investigated by time-resolved absorption spectroscopy. The formation of MV(*+) generated from the one-electron reduction reaction with CO(2)(*-), which is generated from the one-electron oxidation reactions with the photogenerated holes (h(+)), was directly observed. The spectral features of the photogenerated charge carriers and the kinetic analysis of the formation process of MV(*+) revealed that the CO(2)(*-), desorbed from the surface, reacts with MV(2+) via a homogeneous electron-transfer process in the bulk solution.     

A novel disaccharide,wilforibiose from cynanchum wilfordi h(=emsl)

The structure of a novel disaccharide, wilforibiose, isolated from the root of $\text{Cynanchum wilfordi}$ H(=emsl), has been established by spectral data.     

Cyclic strength of imperfectly saturated sands and analysis of liquefaction

The simplified method of analysis to assess liquefaction potential of a given sand deposit is briefly introduced in the first part of this paper. Then, recent advances in the laboratory testing for evaluating liquefaction resistance are described with a particular emphasis on the sand partly saturated with water. As a means to identify the degree of saturation which is applicable for both field deposits and laboratory samples, the use of the longitudinal wave (P-wave) is proposed based on a suite of data obtained from the triaxial tests in the laboratory. It is recommended that the non-destructive P-wave measurements be carried out first to determine the degree of saturation, and then the cyclic triaxial tests involving large destructive strains should be performed to determine the cyclic strength on the same sample of the sand. In order to demonstrate usefulness of the proposed approach, two sets of undisturbed samples were secured from two sites; one is located in Sakai-minato city which has suffered severe liquefaction at the time of the 2000 Tottoriken-Seibu earthquake and the other site is located in Koshigaya city, Saitama, where likelihood of liquefaction to occur in a future earthquake is of major concern. Penetration tests and in-situ velocity logging were also conducted at these two sites. By adjusting the P-wave velocity of the undisturbed samples in the laboratory so as to have the same velocity in the field, the in-situ state of saturation was reproduced in the laboratory samples. Then, the cyclic loading tests were conducted to determine the cyclic strength of intact samples. The results of the laboratory tests as above were incorporated into the simple method of liquefaction analysis described in the first section of this paper. The analysis seems to yield results which are in reasonably good agreement with what was observed at the time of the earthquake.     

Mössbauer Spectroscopic Study of a Mural Painting from Morgadal Grande,Mexico

Hyperfine Interactions - In this study, 57Fe Mössbauer spectroscopy has been applied to fragments of a mural painting excavated at Morgadal Grande, Mexico, to characterize the pigments used. A...     

Trends of optically fed wireless communication systems

Mobile communication systems such as cellular radio and PHS are rapidly penetrating into our real life, and have gained many subscriber numbers. User demands will be growing to higher data rates that support multimedia mobile computing demands, such as graphics and motion pictures. These demands require more band width and/or spectrum utilization efficiency enhancement, and optically fed communication systems are considered to be one of the most powerful solutions. In this paper, the roles, technologies and application examples of optically fed communication systems are described. In the final part, prospects for systems and requirements for photonic devices are mentioned.     

Disposition of ipriflavone (TC-80) in rats and dogs

Oral 14C-ipriflavone was absorbed by rats to give a maximum plasma 14C level at 1.5 h and a half-life of 5.8 h. In dogs, after po dosing, the plasma 14C peaked at 0.5 h, followed by gradual decline. The plasma of both animals contained mostly metabolites, with small amounts of unchanged ipriflavone. In rats, 14C was distributed widely in tissues, with relatively high concns. in the liver, kidney and gut. Distribution in rat thigh bone of unmetabolized ipriflavone was also demonstrated. 14C-Ipriflavone was eliminated mostly as metabolites within 48 and 72 h, respectively, in rats and dogs. Rats excreted more 14C in urine than in feces, whereas the reverse was noted in dogs. Biliary excretion and reabsorption of 14C were also obvious in both animals.